CN109790024A - The method for preparing metal nitride and metal carbides - Google Patents
The method for preparing metal nitride and metal carbides Download PDFInfo
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- CN109790024A CN109790024A CN201780061701.8A CN201780061701A CN109790024A CN 109790024 A CN109790024 A CN 109790024A CN 201780061701 A CN201780061701 A CN 201780061701A CN 109790024 A CN109790024 A CN 109790024A
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Abstract
The method for preparing metal nitride and/or metal carbides, the purposes of metal nitride and/or metal carbides and the metal nitride and/or carbide in catalysis, the optionally processing of catalysis hydrogen optionally according to this method preparation.Optionally, this method comprises: i) making at least one comprising the first metal M of at least one1Metal oxide and include the second metal M of at least one2Cyano metal compound contact to form reaction mixture；And ii) reaction mixture is made to undergo at least 300 DEG C of one section of reaction time of temperature.Optionally, the metal nitride and/or metal carbides are the metal nitride for including tungsten nitride.
Description
Priority claim
This application claims the U.S. Provisional Application No.62/404 submitted on October 5th, 2016, in November, 318 and 2016
The priority of the European application No.16201323.9 submitted for 30th, the disclosure of which are incorporated herein by reference of text.
Invention field
The present invention relates to the method for preparing metal nitride and/or metal carbides, the metal nitride that thus prepares and/
Or the purposes of carbide and these metal nitrides and/or carbide in catalysis.More specifically, but it is non-only, this hair
It is bright to be related to preparing metal nitride and/or metal carbides by least one metal oxide and at least one cyano metal compound
Method.
Background of invention
Metal nitride and metal carbides are the very popular materials for various applications.Especially, nitride metal
Object and metal carbides can be used for being catalyzed hydrogen processing.Alexander and Hargreaves, Chem.Soc.Rev., 2010,39,
4388-4401 is disclosed, and the catalysis behavior of metal nitride and carbide containing molybdenum and tungsten has attracted many concerns, because they
Catalysis behavior and noble metal between have similitude.Tungsten nitride (W2N) have been used for hydrogen processing catalysis (J.G.Chen,
Chem.Rev.1996,96,1477-1498), catalysis oxidation and catalytic oxidation-reduction reaction (ORR) (H.J.Yan, C.G.Tian,
L.Sun,B.Wang,L.Wang,J.Yin,A.P.Wu,H.G.Fu,Energy Environ.Sci.,2014,7,1939–1949；
Y.Liu,W.E.Mustain,ACS Catal.2011,1,212-220；D.Braga,I.G.Lezama,H.Berger,
A.F.Morpurgo,Nano Lett.,2012,12,5218-5223；J.S.Jang,D.J.Ham,E.Ramasamy,J.Lee,
J.S.Lee, Chem.Commun.2010,46,8600-8602).The field of metal nitride and carbide other than catalysis also has
Using.For example, Xiao et al., ACS Nano, 2014,8,7846-7857 are disclosed, and transition metal carbide shows outstanding
Combining properties, such as high-melting-point, high conductivity and thermal conductivity, excellent hardness, excellent mechanical stability and chemical stabilization
Highly corrosion resistant under property and reaction condition.Tungsten nitride coatings on steel significant can be reduced due to its excellent mechanical strength
Corrosion and abrasion (Wear, 2007,262,655-665).Tungsten nitride can also be used as unique dynamic stabilization tungsten carbide phase
Useful precursor because the transformation of tungsten nitride to carbide be local structured (Chem.Soc.Rev., 2010,39,4388-
4401).Metal nitride also provides unique reactivity；For example, the prospect of the nitride crystalline lattice nitrogen as active material for
Mixed metal nitride object such as Co3Mo3Had shown that out for N (S.M.Hunter, D.Mckay, R.I.Smith,
J.S.J.Hargreaves and D.H.Gregory,Chem.Mater.,2010,22,2898-2907,D.Mckay,
D.H.Gregory, J.S.J.Hargreaves, S.M.Hunter and X.-L.Sun, Chem.Commun., 1997,3051-
3053), wherein at most 50% nitrogen can reversibly be added and lose from lattice.The reversible addition of nitrogen is that height takes in nitride
Certainly in composition and phase.Such as Fe3Mo3N and Ni2Mo3N be just not so good as N atom carrier effectively (J.S.J.Hargreaves and
D.Mckay, J.Mol.Catal.A:Chem., 2009,305,125-129).Therefore, to the composition of these mixed metal nitride objects
Synthesis control with phase is desirable.
The conventional synthesis process for preparing nitride includes that metal precursor and ammonia are (typical via the pyroreaction of gas-solid reaction
800 DEG C of ground or more) or the vapor deposition that passes through metal salt precursor.Wriedt, Bull.of Alloy Phase Diagr.,
1989,10 (4), 358-67 are disclosed by making tungsten film and ammonia in high temperature contact come the method for preparing tungsten nitride.Nandi et al.
ACS Appl.Mater.Interfaces, 2014,6,6606-6615 disclose the atomic layer deposition of molybdenum nitride film.Tungsten nitride film
Atomic layer deposition be disclosed in Chem.Mater, 2003,15,2969-2976, WO00/41404 (Gelest) and
Phys.Chem.Chem.Phys., 2015,17,17445-17453.It is draped over one's shoulders by the Tungsten nitride coatings deposition of reactive magnetron sputtering
It is exposed to Wear, 2007,262,655-665.These methods typically provide the material with opposite low surface area, and harsh
Condition hampers the accurate control to granularity.It is often difficult in addition, preparing mixed metal nitride by these methods
Or it is impossible.Recently, Xiao et al., ACS Nano, 2014,8,7846-7857 disclose preparation porous C o3ZnC nanometers
The method of grain, is by under nitrogen atmosphere in 600 DEG C of annealing temperature Zn3[Co(CN)6]2/ polyvinylpyrrolidone nanometer
Sphere precursor.The method for preparing cementite is by thermal decomposition " Prussian blue " (Fe4[Fe(CN)6]3) (Aparicio, C.,
Machala, L. and Marusak, Z., J.Therm.Anal.Calorim.2012,110,661；Mohamed B.Zakaria,
RSC Adv., 2016,6,10341).It is unknown for preparing the similar approach of metal nitride.Certain metal nitrides are low
Temperature using supercritical ammine prepare (J.Mater.Chem., 2004,14,228-32), but the very high pressure of the process requirement and
Professional equipment.
There is still a need for low temperature, inexpensive and general synthetic route prepares various metal nitrides and carbide,
It does not need using profession and/or complicated process equipment.More specifically, it is still desirable to from the starting material preparation being easy to get
The convenience approach of metal nitride and carbide.
Summary of the invention
According in a first aspect, the present invention provides the method for preparing metal nitride and/or metal carbides, this method packet
It includes: i) making at least one comprising the first metal M of at least one1Metal oxide and include the second metal M of at least one2Cyanogen
Base Metal compound is contacted to form reaction mixture；And ii) reaction mixture is made to undergo one section of temperature of at least 300 DEG C
Reaction time.Optionally, this method is the method for preparing metal nitride.Optionally, this method is to prepare metal carbides
Method.
Inventor has surprisingly observed that heating metal oxide and the mixture of cyano metal compound are at least 300 DEG C
Temperature provides particularly convenient and effectively prepares metal nitride and/or gold by precursor be easy to get, relatively inexpensive
Belong to the method for carbide.Especially, the inventors discovered that, method of the invention can be used under relatively mild reaction conditions
Prepare metal nitride and/or metal carbides.In addition, the method for the first aspect of the present invention, which provides, prepares a variety of different gold
Belong to adjustable method of nitride and/or metal carbides, such as is metallized by using different metal oxides and cyano
Object precursor.
According to second aspect, the present invention provides metal nitride and/or carbide, it includes: a) it is selected from consisting of
List the first metal nitride and/or carbide: nitrided iron, cementite, cobalt nitride and cobalt carbide；And b) selected from following
The second metal nitride and/or carbide of the list of composition: tungsten nitride, tungsten carbide, nitridation rhenium and carbonization rhenium.Optionally, should
Metal nitride and/or metal carbides include tungsten nitride and at least one of nitrided iron and cementite, such as are nitrogenized
Tungsten, nitrided iron and cementite, such as W2N、Fe4N and Fe3C.It is possible that such metal nitride and/or carbide are special
Ground can be used as catalyst, and/or can be by particularly convenient route by starting material be easy to get and relatively low cost
Material preparation.
According to the third aspect, the present invention provides the nitride metals prepared by method according to the first aspect of the invention
Object and/or metal carbides, optionally, wherein the metal nitride and/or metal carbides are second party according to the present invention
The metal nitride and/or metal carbides in face.
According to fourth aspect, the present invention provides the metal nitrides of second or third aspect and/or metal carbides to make
For the purposes of catalyst.
Detailed description of the invention
Fig. 1 shows that cyano metal compound and metal oxide precursor and reaction are mixed after various temperature heat the various times
Close infrared (IR) spectrogram of object；
Fig. 2 shows the powder of cyano metal compound and metal oxide precursor and reaction mixture after the heating of various temperature
Last X-ray diffraction pattern；
Fig. 3 shows temperature three hours of 600 DEG C of the mixture experience of cyano metal compound and metal oxide precursor
Scanning electron microscopy (SEM) image of reaction product；
Fig. 4 shows that the side of Fig. 3 image is most of；And
Fig. 5 shows temperature two hours of 600 DEG C of the mixture experience of cyano metal compound and metal oxide precursor
Transmission electron microscopy (TEM) image of reaction product.
Detailed description of the invention
In the present invention, which includes the first metal M of at least one1.Easily, M1For transition metal.Such as this
Used herein, term " transition metal " refers to the element in the area d or f of the periodic table of elements, including periodic table of elements 3-12
Element and group of the lanthanides and actinides in race.M1It may be, for example, the transition metal selected from the area periodic table of elements d, preferably select
From the periodic table of elements the 5th, 6 or 7 races, for example it is selected from the list of consisting of: vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum
(Mo), tungsten (W), manganese (Mn), technetium (Tc) and rhenium (Re).It is possible that in the method for the invention, comprising it is at least one for selected from
First metal M of the transition metal of the race of the 5th, 6 or 71Metal oxide particularly good reacted with cyano metal compound.M1It can
For example selected from the list of consisting of: niobium (Nb), molybdenum (Mo), tungsten (W) and rhenium (Re).It is possible that working as M1For Nb, Mo, W or
When Re, the reaction between the metal oxide and cyano metal compound carries out particularly effective.In certain embodiments,
M1It can be tungsten (W) or rhenium (Re), more specifically tungsten (W).It is possible that working as M1When for W or Re, gained metal nitride and/or
Carbide is particularly useful in such as catalysis.In the specific embodiment, which may include WO3, especially
It is wolframic acid and/or Re2O7, especially perrhenic acid.It is possible that WO3, especially wolframic acid and Re2O7, especially high rhenium
Acid is easily reacted with cyano metal compound to prepare the metal nitride of tungstenic and/or rhenium and/or metal carbides.Into
In the specific embodiment of one step, which may include WO3, especially wolframic acid.
The cyano metal compound being used in the present invention may include dicyan based metallization object, four cyano metal compound, six cyanogen
Base Metal compound and/or eight cyano metal compounds, preferably four cyano metal compound and/or six cyano metal compounds.Preferably,
Cyano metal compound is six cyano metal compounds.It will be appreciated that dicyan based metallization object includes to be coordinated to two cyanide ligands
The metal center of body, four cyano metal compound include the metal center for being coordinated to four cyanide ligands, six cyano metal compounds
Metal center and eight cyano metal compounds comprising being coordinated to six cyanide ligands include to be coordinated to eight cyanide ligands
Metal center.It is possible that four cyano metal compound and/or six cyano metal compounds, such as the metallization of especially six cyano
Object provides cyano metal compound precursor that is particularly effective and being conveniently used for method of the invention.Preferably, when cyano metal
When compound includes dicyan based metallization object, dicyan based metallization object includes copper (Cu), silver-colored (Ag) or golden (Au).Preferably, work as cyanogen
When Base Metal compound includes four cyano metal compound, four cyano metal compound includes nickel (Ni), palladium (Pd) and/or platinum (Pt).It is excellent
Selection of land, when cyano metal compound includes six cyano metal compounds, six cyano metal compounds include titanium (Ti), vanadium (V), chromium
(Cr), manganese (Mn), iron (Fe) and/or cobalt (Co).Preferably, when cyano metal compound includes eight cyano metal compounds, eight cyanogen
Base Metal compound includes molybdenum (Mo).
Preferably, cyano metal compound includes to have formula M3x[M2(CN)y]zMaterial, wherein M2And M3It is identical or different
Metal, especially wherein x be 1-4 integer, especially 1 or 4, preferably y be 4 or 6, and preferably z be 1-3 it is whole
Number, especially 1 or 3.Optionally, 1 x, z 1 and y are 6.Optionally, 4 x, z 3 and y are 6.Easily, M2For
Transition metal.M2It can be selected, for example, from the 8th and 9 races of the periodic table of elements, for example be selected from the list of consisting of: iron (Fe) and cobalt
(Co), Fe (II), Fe (III) and Co (III) are especially selected from.Cyano metal compound anion is especially advantageous with formula [Fe
(II)(CN6)]4 -、[Fe(III)(CN)6]3 -[Co (III) (CN)6]3 -.It is not wishing to be bound by theory, it is believed by the inventors that this
The method of invention is highly suitable for cyano metal compound, which includes diversified different metal as gold
Belong to M3, including, for example, such cyano metal compound, wherein M3(i.e. for alkali metal, alkaline-earth metal, transition metal, rare earth metal
Group of the lanthanides or actinide metals) or periodic table of elements 13-16 race base metal, preferably such cyano metal compound, the wherein gold
Belong to M3For alkali metal, the base metal of the 13rd race of transition metal, the rare earth metal of group of the lanthanides or the periodic table of elements.It will be appreciated that inferior
Metal is the metallic element between the transition metal and metalloid of the periodic table of elements, for example including aluminium (Al), gallium (Ga), indium
(In), thallium (Tl), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb) and bismuth (Bi).M3It can be selected, for example, from the list of consisting of: potassium
(K), iron (Fe), cobalt (Co), yttrium (Y), aluminium (Al), gallium (Ga), lanthanum (La), praseodymium (Pr) and dysprosium (Dy).Preferably, M3For K (I),
Fe (III), Co (III), Y (III), Al (III), Ga (III), La (III), Pr (III) or Dy (III).Preferably, M3It is three
Valence metal cation.As used in this article, term " trivalent metal cation " is the metal cation in 3+ oxidation state.Side
Just, M3For transition metal.M3It can be selected, for example, from the 3rd race, the 8th race, the 9th race or the group of the lanthanides of the periodic table of elements.Specifically implementing
In scheme, M3It can be Fe (III) or Co (III).In this application, M2And M3It may be the same or different, it is advantageously that identical.Cyanogen
The suitable example of Base Metal compound includes Fe4[Fe(CN)6]3、K3[Fe(CN)6]、Y[Fe(CN)6]、Al[Fe(CN)6]、La
[Fe(CN)6]、Pr[Fe(CN)6]、Dy[Fe(CN)6]、Co[Co(CN)6]、Y[Co(CN)6]、Al[Co(CN)6]、La[Co
(CN)6] and/or K3[Co(CN)6], especially Fe4[Fe(CN)6]3And/or Co [Co (CN)6]。
In the method for the invention, the molar ratio of the metal oxide in contact procedure i) and cyano metal compound can range
In 20:1-1:20, such as 10:1 to 1:10, such as 10:1 to 1:5, it is especially selected from 10:1-1:1.Additionally or alternatively, it contacts
M in step i)1: M2+M3Molar ratio can range in 5:1-1:5, such as 3:1-1:3, such as 2:1-1:2, especially about 1:1.
It is possible that limited molar ratio helps avoid the unnecessary waste of excess material.
Optionally, the step of contacting the metal oxide to form reaction mixture with the cyano metal compound includes shape
At the immixture of metal oxide and cyano metal compound.It is possible that forming metal oxide and cyano metal compound
Immixture improve reaction efficiency, thus provide the precursor to desired metal nitride and/or metal carbides
Better conversion.At least one metal oxide and the contact of cyano metal compound can under presence or absence of solvent into
Row.If solvent exists, water, organic solvent and its mixture, especially water can be typically chosen from.It will be appreciated that using
Water is as at least part of solvent, or does not use solvent, it is possible to provide particularly environmentally friendly and comparatively safe method is made
Standby metal nitride and/or metal carbides, such as use less organic solvent.
For example, in one embodiment, the cyano metal compound and the metal oxide can provide in solid form, and
And the contact procedure i) for forming reaction mixture can be carried out by the dry-mixed cyano metal compound and the metal oxide, such as
Wherein the cyano metal compound and the metal oxide are provided in the form of crystal or powder.It will be appreciated that term " dry-mixed "
Refer to the method for wherein mixing material in the case where substantially not using solvent.It will also be appreciated that term is " dry
It is mixed " it include any mixed method for merging two kinds of solids without using liquid solvent, therefore be not excluded for, for example,
Use the solid material comprising the compound with solvate cocrystallization.The suitable example of dry blend process include grinding (such as
Ball milling) and basic skills, for example use the solid mixing of pestle and mortar.
In another embodiment, the cyano metal compound and the metal oxide can merge in the presence of the solvent.Especially
It is that cyano metal compound used in method of the invention can be provided in the form of cyano gel, wherein the cyano gel packet
Containing mixture below: a) the cyano metal compound and b) at least part of solvent.As used in this article, term " cyanogen
Base gel " refers to the mixture of cyano metal compound and solvent, such as by by solvent and cyano metal compound (such as powder shape
Formula) merging, and gained mixture is stirred to be formed.Mixing can using any suitable method realize, for example, by using turn
Magnetic stirring apparatus on sub- platform.It is possible that the cyano gel be solution, gel or solid form (such as solid powder or
Crystalline material, wherein solvent is by being absorbed into cyano metal compound).It is possible that when cyano metal compound is to include cyanogen
When the form of the cyano gel of Base Metal compound and at least partly solvent provides, the metal oxide and cyano metallization are formed
The step of reaction mixture of object, can be carried out in a manner of particularly effective and is flat-footed.For example, it is possible that cyano gel
Use allow to be formed in the step of forming reaction mixture the cyano metal compound and the metal oxide especially closely
Mixture.It will be appreciated that using the cyano gel comprising cyano metal compound and water can provide it is particularly environmentally friendly and
The comparatively safe method for preparing metal nitride and/or metal carbides, such as by using less organic solvent.At this
In the specific embodiment of sample, when the step of contacting the metal oxide to form reaction mixture with the cyano metal compound
When immixture including forming metal oxide and cyano metal compound, the cyano metal compound is with the shape of cyano gel
Formula, provides preferably in the form of the cyano gel comprising cyano metal compound and the mixture of solvent and the metal aoxidizes
Object provides preferably in the form of solid such as crystal or powder.The mixing of the cyano gel and the metal oxide can use
Any suitable method realizes that, for example, by using the magnetic stirring apparatus on ball milling and rotor platform, this depends on reaction mixture
Viscosity.The mixing optionally carries out under there are the solvent of other amount, if the cyano gel only includes a part of molten
If agent.
The method of the first aspect of the present invention includes the temperature for making the reaction mixture undergo at least 300 DEG C, is preferably passed through
Go through the temperature of the decomposition temperature equal to or higher than the cyano metal compound.As used in this article, " decomposition temperature " of substance is
The substance decomposition forms the temperature of the different substance of one or more chemistry.For example, reaction mixture can undergo at least 400 DEG C,
Such as at least 500 DEG C, especially at least 600 DEG C of temperature.Suitable temperature range may include 300 to 1000 DEG C, for example, 400 to
900 DEG C, especially 500 to 800 DEG C, such as 600 to 700 DEG C of temperature.It is possible that higher temperature is convenient for the cyano metal
It is reacted faster between compound and the metal oxide.It is possible that reaction mixture temperature experienced is to provide effectively
Reaction speed and avoid the balance between nitride and/or the undesired thermal decomposition of carbide products.It is still possible that reaction
Mixture temperature experienced is to provide effective reaction speed and avoids the need for the balance between high cost special equipment.
Reaction time is typically at most 48 hours, such as at most 24 hours, and especially up to 12 hours.For example, reaction
Time can be 10 minutes to 48 hours, such as 20 minutes to 24 hours, be especially selected from 30 minutes to 12 hours.It is possible that anti-
It is the enough time for allowing the desired metal nitride of reasonable amount and/or metal carbides to be formed between seasonable and prevent or reduce
Desired metal nitride and/or metal carbide products and/or the metal oxide and/or cyano metal compound precursor are not
Balance between desired thermal decomposition.
In the preferred embodiment of the third aspect of the present invention, the metal nitride and/or metal carbides include
The material of list selected from consisting of: tungsten nitride, molybdenum nitride, niobium nitride nitrogenize rhenium, tungsten carbide, molybdenum carbide, niobium carbide and carbon
Change rhenium, especially tungsten nitride or carbonization rhenium.For example, the metal nitride and/or metal carbides are metal nitride, preferably nitrogen
Change tungsten, such as W2N.Optionally, the metal nitride and/or carbide are metal carbides, preferably carbonization rhenium.Of the invention
The metal nitride and/or metal carbides of three aspects also may include at least two different metals, such as such as of the invention the
First metal M defined in one side1, it is especially selected from the first metal of the list of consisting of: W, Mo, Nb and Re, and
Such as the second metal M defined in the first aspect of the invention2, especially it is selected from the second metal of the list of consisting of: Fe
And Co.For example, the metal nitride and/or metal carbides of the third aspect of the present invention may include a) nitrided iron and/or carbonization
Iron or at least one of cobalt nitride and/or carbide, especially nitrided iron and/or cementite；And b) tungsten, molybdenum, niobium or rhenium
Nitride and/or at least one of carbide, especially tungsten nitride or carbonization rhenium, especially tungsten nitride.Further special
In fixed embodiment, the metal nitride and/or metal carbides of second or third aspect of the invention include tungsten nitride, with
And at least one of nitrided iron and cementite, such as tungsten nitride, nitrided iron and cementite, such as W2N、Fe4N and Fe3C.It may
, these metal nitrides and/or carbide be particularly used as catalyst, and/or can be by by be easy to get and phase
Particularly convenient route preparation to the starting material of low cost.
The metal nitride and/or metal carbides of second or third aspect of the invention are typically crystalline material or powder
The form at end.
Optionally, the metal nitride and/or metal carbides include Fe4N and the metal nitride and/or carbonization
The powder X-ray diffraction pattern of object includes the peak with following 2 θ value: 23.45,33.36,41.17,47.91,53.99,
59.64,70.06,75.02,79.87,84.65,94.03,98.87 and 108.52, the powder X-ray diffraction pattern use with
Under diffractometer on collect: Cu K α,It radiates source range and uses 0.02 ° of step in 5 °≤2 θ≤70 °
Long, gate time is 1s/ step, 1/4 jiao of entrance slit, the electric current of 45kv and 40mA.
Additionally or alternatively, the metal nitride and/or metal carbides optionally include Fe3C and the metal nitrogen
Compound and/or the powder X-ray diffraction pattern of carbide include the peak with following 2 θ value: 26.19,31.36,33.93,
35.89,41.78,43.92,47.05,50.08,53.89,55.66,59.18,60.46,61.80,63.20,67.31,
76.81,79.87,83.22,86.90,91.00 and 95.57, the powder X-ray diffraction pattern is using on diffractometer below
It collects: Cu K α,It radiates source range and uses 0.02 ° of step-length, gate time 1s/ in 5 °≤2 θ≤70 °
Step, 1/4 jiao of entrance slit, the electric current of 45kv and 40mA.
Additionally or alternatively, the metal nitride and/or metal carbides include W2N, and the metal nitride and/
Or the powder X-ray diffraction pattern of carbide includes the peak with following 2 θ value: 37.73,43.85,63.73,76.51,
80.59,96.68,108.86 and 113.14, which collects on using diffractometer below: Cu K α, Source range is radiated in 5 °≤2 θ≤70 ° using 0.02 ° of step-length, gate time is 1s/ step, and 1/4 jiao enters
Penetrate slit, the electric current of 45kv and 40mA.
According to the fourth aspect of the invention, metal nitride of the invention and/or metal carbides can be used to form (or make
For) hydrogen processing catalyst.It will be appreciated that hydrogen processing catalyst can for example be used for a variety of different hydrogen processing applications, such as hydrogenate
Cracking, hydrodenitrogeneration, hydrodesulfurization, hydrofinishing, hydroforming plus hydrogen and/or hydrotreating.Preferably, catalyst is to add
Hydrogen, hydrodenitrogeneration and/or Hydrobon catalyst.It is possible that the metal nitride catalyst of nitrogen tungsten particularly can be used
Make hydrotreating catalyst, such as is used as and adds hydrogen, hydrodenitrogeneration and/or Hydrobon catalyst.For example, it is possible that this is urged
Agent is the catalyst of the hydrogenolysis for cycloalkane.
Of course it is to be understood that the feature about one aspect of the present invention description can be incorporated into other aspects of the present invention
In.For example, the metal carbides and/or nitride of second or third aspect of the invention may include with reference to of the invention first
Any feature of the method description of aspect, vice versa.
The embodiment of the present invention
The following examples illustrate the invention.Many modifications and variations are possible, and it will be understood that in appended claims
In the range of, the present invention can be different from the mode specifically described herein and implement.
Powder X-ray RD data are collected using original position PANalytical X-ray diffractometer, under nitrogen and oxygen stream, are furnished with
Cu KαRadiation, and in the range of 5 °≤2 θ≤70 ° (step-length: 0.02 °, gate time: 1s/ step, 1/4
The electric current of angle entrance slit, 45kv and 40mA).
IR data use Vertex 80, and Praying Mentis IR spectrometer is collected, and drift mode, 128 times background is swept
It retouches, 128 Sample Scans, 64 FW scannings second-best and 64 BW scannings second-best.
" Prussian blue " (Fe4[Fe(CN)6]3) it is obtained from Sigma-It is dark blue/purple crystal powder, directly
Connect use.Fe4[Fe(CN)6]3Infrared spectroscopy track D is shown as in Fig. 1.Fe4[Fe(CN)6]3X-ray diffractogram of powder
Case is shown as track D in Fig. 2.
Wolframic acid (H2WO4) it is obtained from Sigma-It is yellowish orange powder (99% purity), is directly used.
H2WO4Infrared spectroscopy track E is shown as in Fig. 1.H2WO4Powder X-ray diffraction pattern track E is shown as in Fig. 2.
Yttrium nitrate (III) hydrate (Y (NO3)3.xH2) and six cyano ferric acid (II) potassium (K O3[Fe(CN)6]) be obtained from
Signma-
The typical process for preparing mixed transition metal cyano metal compound is as follows: by Y (NO3)3.xH2O (10mmol) adds
Enter K3[Fe(CN)6] solution of (10mmol) in water (50mL), obtain brown color precipitating.The precipitating is collected by filtration and uses water
(20mL) is washed to remove by-product KNO3.Obtained solid is dried overnight at 120 DEG C, obtains the Y [Fe of about 75% yield
(CN)6].To Y [Fe (CN)6] sample of product tested by powder x-ray diffraction to confirm its feature.
Unless otherwise indicated, for the cyano gel of following embodiment by by cyano metal compound and solvent (typically
Fe4[Fe(CN)6]3And water) merge in beaker and prepared by hand operated mixing mixture.
Unless otherwise indicated, the metal nitride/Carbide Sample prepared in following embodiment is the shape with crystalline material
What formula obtained.
Ce/ZrO2(Ceria-zirconia), vulcanization ZrO2(sulfidation-oxidation zirconium) and W/ZrO2(tungsten zirconium oxide) is from quotient
Industry suppliers obtain Bronsted acidity carrier and non-modified direct use.
Embodiment 1:
By H2WO4(5g) and Fe4[Fe(CN)6]3(2.4g) is with H2WO4Compare Fe4[Fe(CN)6]3The molar ratio of 7:1 (provides
The 1:1 molar ratio of W:Fe) use pestle and mortar to pass through solid mixing to merge to form close solid mixture.Keep gained mixed
The sample (2g) for closing object undergoes temperature one hour of 600 DEG C under nitrogen atmosphere to form metal nitride/Carbide Sample X1a.
The infrared spectroscopy of sample X1a is shown as track C in Fig. 1.Then sample X1a is made to undergo 600 DEG C of temperature another under nitrogen atmosphere
Outer 12 hours are to form metal nitride/Carbide Sample X1b.The infrared spectroscopy sample of X1b is shown as track B in Fig. 1.
The other sample (2g) of mixture is set to undergo temperature one hour of 750 DEG C under nitrogen atmosphere to form metal nitride/carbonization
Object sample X2.The infrared spectroscopy of sample X2 is shown as track A in Fig. 1.
The IR data provided in Fig. 1 are shown, work as Fe4[Fe(CN)6]3With H2WO4Lack CN when being heated after solid mixing
(CN stretching frequency is about 2100cm to stretching frequency-1) and W=O stretching frequency (WO stretching frequency is about 950cm-1), thus
Show that cyano metal compound and metal oxide precursor are changed into desired metal nitrogen by at least part of disappearance in the peak CN and WO
Compound/carbide.It is believed that the new material formed is largely that IR is inert.
Embodiment 2:
H2WO4(5g) and Fe4[Fe(CN)6]3(2.4g) is with H2WO4Compare Fe4[Fe(CN)6]37:1 molar ratio (provide W:
The 1:1 molar ratio of Fe) use pestle and mortar to pass through solid mixing to merge to form close solid mixture.Mix gained
The sample (2g) of object undergoes temperature one hour of 450 DEG C under nitrogen atmosphere to form metal nitride/Carbide Sample X3.Sample
The powder X-ray diffraction pattern of X3 is shown as track C in Fig. 2.Pass through the other sample (2g) of mixture under nitrogen atmosphere
Temperature one hour of 600 DEG C is gone through to form metal nitride/Carbide Sample X4.The infrared spectroscopy of sample X4 is shown in Fig. 2
For track B.The other sample (0.1g) of mixture is set to undergo temperature one hour of 750 DEG C under nitrogen atmosphere to form metal nitrogen
Compound/Carbide Sample X5.The infrared spectroscopy of sample X5 is shown as track A in Fig. 2.
Tungsten nitride (W2N peak index) is indicated by being marked as 100,101,102,220 and 201 line in Fig. 2
(referring to J.Mater.Chem., the data announced in 2011,21,10761-66), shows W2N is present in sample X3 into X5.Sample
Product X3 to X5 also contains other metal nitrides and metal carbides, such as Fe4N、C3N4、Fe3C and Fe2O3。W2N、Fe4N and
Fe32 peak the θ indexes of C are listed in Table 1 below that (product and by-product are by comparing every kind of independent substance-W2The literature value of N confirms:
Fiala, Central Research Institute, SKODA, Czechos lovakia, Private Communication
(1973)；Fe4N:Jack.Proc.R.Soc.London, Ser.A 195,34 (1948)；Fe3C:
Konobejewski.Z.Kristallogr., Kristallgeom., Kristallphys., Kristallchem.72,386
(1929)).It is visible under the resolution ratio for the powder X-ray diffraction pattern that the peak listed in not all table 1 is all shown in Fig. 2.
Table 1- is present in W of the sample X3 into X52N、Fe4N and Fe3The X-ray powder diffraction peak of C indexes
The powder X-ray diffraction pattern of Fig. 2 shows after heating relatively short time quantum at a temperature of mild, metal
Oxide and cyano metal compound precursor have been transformed into metal nitride and carbide.
Embodiment 3:
By H2WO4(2.5g) and cyano gel (include Fe4[Fe(CN)6]3(1.2g) and water (50mL)) (provide the 1 of W:Fe:
1 molar ratio) with H2WO4Compare Fe4[Fe(CN)6]3The molar ratio of 7:1 mixes in 250mL beaker (provides the 1:1 of W:Fe
Molar ratio) to form immixture.The sample (3g) of mixture obtained by making undergoes temperature three hours of 600 DEG C under nitrogen atmosphere
To form metal nitride/Carbide Sample X6.Scanning electron microscopy (SEM) image for shooting sample X6, shows plate table
Face form (the case where SEM image is shown in Fig. 3 and 4).
Embodiment 4:
By H2WO4(2.5g) and cyano gel (include Fe4[Fe(CN)6]3(1.2g) and water (50mL)) with H2WO4Compare Fe4
[Fe(CN)6]3It is close mixed to be formed that the molar ratio of 7:1 mixes (the 1:1 molar ratio for providing W:Fe) in 250mL beaker
Close object.The sample (3g) of gained mixture is set to undergo temperature three hours of 600 DEG C under nitrogen atmosphere to form metal nitride/carbon
Compound sample X7.The transmission electron microscope image for shooting sample X7, being shown without apparent mutually separation, (the case where image, is shown in
Fig. 5).
Embodiment 5:
By untreated Fe4[Fe(CN)6]3(P1) and H2WO4(T1) sample is separately carried out using X-Ray Photoelectron Spectroscopy
Analysis, result are given in Table 2.Make Fe4[Fe(CN)6]3Other sample undergo temperature one hour of 600 DEG C to obtain
Sample P 2.Sample P 2 is also analyzed using X-Ray Photoelectron Spectroscopy, and result is given in Table 2.
H2WO4(5g) and Fe4[Fe(CN)6]3(2.4g) is with H2WO4Compare Fe4[Fe(CN)6]3The molar ratio of 7:1 uses pestle
(the 1:1 molar ratio for providing W:Fe) is merged to form close solid mixture by solid mixing with mortar.Mix gained
350 DEG C of the temperature that undergoes under nitrogen atmosphere of the sample (2g) of object one hour to form metal nitride/Carbide Sample X8.Make to mix
It closes the further sample of object (1g) and undergoes temperature one hour of 450 DEG C under nitrogen atmosphere to form metal nitride/carbide sample
Product X9.So that the further sample of mixture (1g) is undergone 600 DEG C of temperature one hour under nitrogen atmosphere with formed metal nitride/
Carbide Sample X10.The further sample of mixture (1g) is set to undergo temperature two hours of 600 DEG C under nitrogen atmosphere to form gold
Belong to nitride/Carbide Sample X11.The further sample of mixture (1g) is set to undergo 600 DEG C of temperature three small under nitrogen atmosphere
When to form metal nitride/Carbide Sample X12.The further sample of mixture (1g) is set to undergo 750 DEG C under nitrogen atmosphere
Temperature one hour to form metal nitride/Carbide Sample X13.Each sample X8 to X13 is used into x-ray photoelectron light
Spectrum Analysis, result are given in Table 2.
Table 2- tracks H2WO4And Fe4[Fe(CN)6]3Reaction X-Ray Photoelectron Spectroscopy analysis
The X-Ray Photoelectron Spectroscopy that is provided in table 2 the result shows that, by metal oxide and cyano metal compound precursor
Mixture forms metal nitride as the mixture is heated.It should be noted that XPS is the technology of surface specificity,
It only provides on the surface for accounting for sample relatively small fraction that there are the instructions of what material.Therefore, it does not provide the entirety of sample
The instruction of material composition, therefore integrality or otherwise qualitative assessment that nitride product is formed are not provided.
Embodiment 6:
It is urged in hydrogenolysis according to what is be given below using the product of the sample X6 prepared in embodiment 3 as catalyst cycloalkane
Agent test is tested.
Test 1
By sample X6 (0.2g) and EHC-50 (API class ii base-material includes about 80% naphthenic ring and about 20% aromatic ring)
(3g) merges, and in a kettle in H2It is 300 DEG C small up to 6 with being stirred and heated to for 600RPM under pressure (900psig, 62barg)
When.
Test 2
By sample X6 (0.2g), about 10%Ce/ZrO2(API class ii base-material includes about 80% ring by (0.2g) and EHC-50
Alkane and about 20% aromatic ring) (3g) merging, and in a kettle in H2Stirring with 600RPM under pressure (900psig, 62barg)
It mixes and is heated to 300 DEG C up to 6 hours.
Test 3
By sample X6 (0.2g), vulcanization ZrO2(about 2.3%S) (0.2g) and EHC-50 (API class ii base-material, comprising about
80% cycloalkane and about 20% aromatic ring) (3g) merging, and in a kettle in H2Under pressure (900psig, 62barg) with
600RPM's is stirred and heated to 300 DEG C up to 6 hours.
Test 4
By sample X6 (0.2g), about 15%W/ZrO2(API class ii base-material includes about 80% ring by (0.2g) and EHC-50
Alkane and about 20% aromatic ring) merge, and in a kettle in H2Added under pressure (900psig, 62barg) with the stirring of 600RPM
Heat is to 300 DEG C up to 6 hours.
The product for testing 1-4 is analyzed by GCMS and SFC (supercritical fluid chromatography).Data from GCMS with
SFC data are consistent, show that cycloalkane is more in charging but less in the product.The data are also shown that alkane in the product
It is more but less in charging.The result of catalytic test illustrates that X6 catalyst is for being for isoparaffin by cycloalkanes
It is effective.
In description in front, when referring to the integer or element with known, apparent or foreseeable equivalent,
These equivalents are incorporated to herein, as individually illustrating.Claim be should refer to determine true scope of the invention, be somebody's turn to do
Range should be interpreted to include any such equivalent.Reader will also be understood that be described as it is preferred, advantageous, convenient etc.
Integer of the invention or be characterized in optional, and do not limit the range of independent claims.Also, it is to be understood that
Although this optional integer or feature in certain embodiments of the invention may it is beneficial, may not be it is desired, because
This may be lacked in other embodiments.
Additionally or alternatively, the present invention relates to:
Embodiment 1: the method for preparing metal nitride and/or metal carbides, this method comprises:
I) make at least one comprising the first metal M of at least one1Metal oxide and include the second metal M of at least one2
Cyano metal compound contact to form reaction mixture；And
Ii the reaction mixture) is made to undergo at least 300 DEG C of one section of reaction time of temperature.
Embodiment 2: according to the method for embodiment 1, wherein M1For transition metal, preferably wherein M1Selected from element week
Phase table the 5th, 6 or 7 races.
Embodiment 3: according to the method for embodiment 1 or 2, wherein M1Selected from the list being made up of: W, Re, Nb and
Mo；It is especially selected from W and Re.
Embodiment 4: according to the method for any foregoing embodiments, wherein the metal oxide includes WO3, especially tungsten
Acid；And/or wherein the metal oxide includes Re2O7, especially perrhenic acid.
Embodiment 5: according to the method for any foregoing embodiments, wherein the cyano metal compound includes dicyan Base Metal
Compound, four cyano metal compound, six cyano metal compounds and/or eight cyano metal compounds, preferably four cyano metal compound and/or
Six cyano metal compounds.
Embodiment 6: according to the method for any foregoing embodiments, wherein the cyano metal compound includes to have formula M3 x
[M2(CN)y]zMaterial, wherein M2And M3For identical or different metal, preferably wherein x is the integer of 1-4, and preferably y is 4
Or 6, and preferably z is the integer of 1-3, more preferably wherein x is that 1, z is 1 and y is 6 or x is that 4, z is 3 and y is 6.
Embodiment 7: according to the method for any foregoing embodiments, wherein M2For transition metal, preferably wherein M2It is selected from
8th and 9 races of the periodic table of elements.
Embodiment 8: according to the method for any foregoing embodiments, wherein M2Selected from the list being made up of: Fe
(II), Fe (III) and Co (III).
Embodiment 9: according to the method for any embodiment 6-8, wherein M3For transition metal, preferably wherein M3It is selected from
The 3rd race, the 8th race, the 9th race or the group of the lanthanides of the periodic table of elements.
Embodiment 10: according to the method for any one of embodiment 6-8, wherein M3Selected from the list being made up of: K
(I), Fe (III), Co (III), Y (III), Al (III), Ga (III), La (III), Pr (III) and Dy (III), are preferably selected
From the list of consisting of: Fe (III) and Co (III).
Embodiment 11: according to the method for any foregoing embodiments, wherein the cyano metal compound includes Fe4[Fe
(CN)6]3, K3[Fe(CN)6], Y [Fe (CN)6], Al [Fe (CN)6], La [Fe (CN)6], Pr [Fe (CN)6], Dy [Fe (CN)6],
Co[Co(CN)6], Y [Co (CN)6], Al [Co (CN)6], La [Co (CN)6] and/or K3[Co(CN)6], preferably Fe4[Fe(CN)6]3
And/or Co [Co (CN)6]。
Embodiment 12: according to the method for any foregoing embodiments, wherein metal oxide and cyanogen in contact procedure i)
The molar ratio of Base Metal compound is 10:1 to 1:10, preferably 10:1 to 1:5, more preferable 10:1 to 1:1.
Embodiment 13: according to the method for any foregoing embodiments, object and cyano wherein are oxidized metal in step i)
The step of contact of metal compound is to form reaction mixture includes the close mixing to form metal oxide and cyano metal compound
Object, optionally in the presence of the solvent.
Embodiment 14: according to the method for embodiment 13, wherein the solvent is selected from water, organic solvent and their mixing
Object, more preferably wherein the solvent is water.
Embodiment 15: according to the method for any foregoing embodiments, wherein the cyano metal compound and the metal are aoxidized
Object merge in the presence of the solvent and wherein the cyano metal compound is provided in the form of cyano gel, the cyano gel comprising with
Under mixture: a) the cyano metal compound and b) at least part of solvent.
Embodiment 16: according to the method for any one of embodiment 1-13, wherein the cyano metal compound and the metal oxygen
Compound provides in solid form, and wherein contact procedure i) includes being aoxidized the metal using dry blend process, especially ball milling
Object merges with the cyano metal compound.
Embodiment 17: according to the method for any foregoing embodiments, wherein the reaction mixture is made to undergo at least 400
DEG C, such as at least 500 DEG C, especially at least 600 DEG C of temperature.
Embodiment 18: according to the method for any foregoing embodiments, wherein the reaction mixture is made to undergo 300 to 1000
DEG C, such as the temperature of 400 to 900 DEG C, especially 500 to 800 DEG C.
Embodiment 19: according to the method for any foregoing embodiments, wherein the reaction time is at most 48 hours, such as
At most 24 hours, especially up to 12 hours.
Embodiment 20: according to the method for any foregoing embodiments, wherein the reaction time is 10 minutes to 48 hours,
Such as 20 minutes to 24 hours, it is especially selected from 30 minutes to 12 hours.
Embodiment 21: metal nitride and/or metal carbides, it includes:
A) the first metal nitride and/or carbide of the list selected from consisting of: nitrided iron, cementite, cobalt nitride
And cobalt carbide；And
B) the second metal nitride and/or carbide of the list selected from consisting of: tungsten nitride, tungsten carbide, nitridation rhenium
With carbonization rhenium.
Embodiment 22: according to the metal nitride and/or metal carbides of embodiment 21, it includes tungsten nitride, with
And at least one of nitrided iron and cementite.
Embodiment 23: according to the metal nitride and/or metal carbides of embodiment 21 or embodiment 22, root
It is prepared according to the method for any one of embodiment 1-20.
Embodiment 24: metal nitride and/or metal carbides, according to the method system of any one of embodiment 1-20
It is standby.
Embodiment 25: according to the metal nitride and/or metal carbides of embodiment 24, the wherein metal nitride
And/or metal carbides include at least two different metals, especially the first metal M of the list selected from consisting of1: W,
Mo, Nb and Re；And the second metal M of the list selected from consisting of2: Fe and Co.
Embodiment 26: according to the metal nitride and/or metal carbides of embodiment 24 or embodiment 25, packet
Containing selected from consisting of list material: tungsten nitride, molybdenum nitride, niobium nitride, nitrogenize rhenium, tungsten carbide, molybdenum carbide, niobium carbide and
Be carbonized rhenium, preferably tungsten nitride and carbonization rhenium.
Embodiment 27: according to the metal nitride and/or metal carbides of any one of embodiment 24-26, it includes
Tungsten nitride and at least one of nitrided iron and cementite.
Embodiment 28: according to the metal nitride and/or metal carbides of any one of embodiment 21-27, wherein should
Metal nitride and/or metal carbides include Fe4N and the wherein powder x-ray diffraction of the metal nitride and/or carbide
Pattern includes the peak with following 2 θ value: 23.45,33.36,41.17,47.91,53.99,59.64,70.06,75.02,
79.87,84.65,94.03,98.87 and 108.52, which collects on using diffractometer below:
Cu K α,Source range is radiated in 5 °≤2 θ≤70 °, using 0.02 ° of step-length, gate time 1s/
Step, 1/4 jiao of entrance slit, the electric current of 45kv and 40mA.
Embodiment 29: according to the metal nitride and/or metal carbides of any one of embodiment 21-28, wherein should
Metal nitride and/or metal carbides include Fe3C and the wherein powder x-ray diffraction of the metal nitride and/or carbide
Pattern includes the peak with following 2 θ value: 26.19,31.36,33.93,35.89,41.78,43.92,47.05,50.08,
53.89,55.66,59.18,60.46,61.80,63.20,67.31,76.81,79.87,83.22,86.90,91.00 Hes
95.57, which collects on using diffractometer below: Cu K α,Radiation
Source range is in 5 °≤2 θ≤70 ° using 0.02 ° of step-length, and gate time is that 1s/ is walked, 1/4 jiao of entrance slit, 45kv, and
The electric current of 40mA.
Embodiment 30: according to the metal nitride and/or metal carbides of any one of embodiment 21-28, wherein should
Metal nitride and/or metal carbides include W2N and the wherein powder x-ray diffraction of the metal nitride and/or carbide
Pattern includes the peak with following 2 θ value: 37.73,43.85,63.73,76.51,80.59,96.68,108.86 and 113.14,
The powder X-ray diffraction pattern is collected on using diffractometer below: Cu K α, Radiation source range exists
Using 0.02 ° of step-length, gate time is 1s/ step, 1/4 jiao of entrance slit, the electric current of 45kv and 40mA for 5 °≤2 θ≤70 °.
Embodiment 31: according to the metal nitride of any one of embodiment 21-30 and/or metal carbides as catalysis
The purposes of agent.
Embodiment 32: the purposes of embodiment 31, wherein the catalyst be hydrogen handle catalyst, preferably plus hydrogen, plus
Hydrogen denitrogenation and/or Hydrobon catalyst.
Claims (21)
1. the method for preparing metal nitride and/or metal carbides, this method include:
I) make at least one comprising the first metal M of at least one1Metal oxide and include the second metal M of at least one2Cyanogen
Base Metal compound is contacted to form reaction mixture, and wherein the cyano metal compound includes dicyan based metallization object, four cyano gold
Belong to compound, six cyano metal compounds and/or eight cyano metal compounds；And
Ii the reaction mixture) is made to undergo at least 300 DEG C of one section of reaction time of temperature.
2. according to the method described in claim 1, wherein M1For the transition metal selected from the periodic table of elements the 5th, 6 or 7 races.
3. according to the method described in claim 2, wherein M1Selected from the list being made up of: W, Re, Nb and Mo；It is especially selected from W
And Re.
4. according to the method described in claim 1, wherein the metal oxide includes WO3And/or wherein the metal oxide includes
Re2O7。
5. according to the method described in claim 1, wherein the cyano metal compound is four cyano metal compound and/or six cyano gold
Belong to compound.
6. according to the method described in claim 4, wherein the cyano metal compound includes having formula M3 x[M2(CN)y]zMaterial,
Wherein M2And M3For identical or different metal, wherein x is the integer of 1-4, and y is the integer that 4 or 6 and z is 1-3.
7. according to the method described in claim 6, wherein x is 1, z is 1 and y is 6 or x is 4, z is 3 and y is 6.
8. method according to claim 1 to 6, wherein M2For selected from the transition of the periodic table of elements the 8th and 9 races gold
Belong to.
9. method according to claim 1 to 6, wherein M2Selected from the list being made up of: Fe (II), Fe
(III) and Co (III).
10. according to the method described in claim 6, wherein M3Selected from the list being made up of: K (I), Fe (III), Co
(III), Y (III), Al (III), Ga (III), La (III), Pr (III) and Dy (III).
11. according to the method described in claim 6, wherein M3Selected from the list being made up of: Fe (III) and Co (III).
12. according to the method described in claim 1, wherein the cyano metal compound includes Fe4[Fe(CN)6]3、K3[Fe(CN)6]、
Y[Fe(CN)6]、Al[Fe(CN)6]、La[Fe(CN)6]、Pr[Fe(CN)6]、Dy[Fe(CN)6]、Co[Co(CN)6]、Y[Co
(CN)6]、Al[Co(CN)6]、La[Co(CN)6] and/or K3[Co(CN)6]。
13. according to the method described in claim 1, wherein the cyano metal compound includes Fe4[Fe(CN)6]3And/or Co [Co
(CN)6]。
14. according to the method described in claim 1, wherein in contact procedure i) metal oxide and cyano metal compound mole
Than for 10:1 to 1:10.
15. according to the method described in claim 1, wherein by the cyano metal compound and the metal oxide solvent presence
Lower merging, and wherein the cyano metal compound is provided in the form of cyano gel, which includes mixture below: a)
The cyano metal compound and b) at least part of solvent.
16. according to the method described in claim 1, wherein the cyano metal compound and the metal oxide mention in solid form
For, and wherein contact procedure i) includes being merged the metal oxide with the cyano metal compound using dry blend process.
17. according to the method described in claim 1, wherein making temperature 10 minutes of 300 to 1000 DEG C of reaction mixture experience
To 48 hours reaction time.
18. metal nitride and/or metal carbides, it includes:
A) the first metal nitride and/or carbide of the list selected from consisting of: nitrided iron, cementite, cobalt nitride and carbon
Change cobalt；And
B) the second metal nitride and/or carbide of the list selected from consisting of: tungsten nitride, tungsten carbide, nitridation rhenium and carbon
Change rhenium.
19. metal nitride according to claim 18 and/or metal carbides are by described in claim 1
Method preparation.
20. metal nitride and/or metal carbides comprising tungsten nitride and at least one of nitrided iron and cementite.
21. the application method of metal nitride described in claim 18 and/or carbide, wherein the metal nitride and/or
Carbide is used as hydrogenation treatment plus hydrogen, hydrodenitrogeneration and/or Hydrobon catalyst.
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| US201662404318P | 2016-10-05 | 2016-10-05 | |
| US62/404,318 | 2016-10-05 | ||
| EP16201323 | 2016-11-30 | ||
| EP16201323.9 | 2016-11-30 | ||
| PCT/US2017/051054 WO2018067276A1 (en) | 2016-10-05 | 2017-09-12 | Method for producing metal nitrides and metal carbides |
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| CN109790024A true CN109790024A (en) | 2019-05-21 |
| CN109790024B CN109790024B (en) | 2023-04-14 |
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| EP (1) | EP3523240B1 (en) |
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| EP3622003A1 (en) * | 2017-05-10 | 2020-03-18 | Dow Global Technologies LLC | Polyether polymerization process |
| CN109437126A (en) * | 2018-10-29 | 2019-03-08 | 福州大学 | A kind of method and application of simple synthesis VN hollow sphere |
| CN113083303A (en) * | 2019-12-23 | 2021-07-09 | 黑龙江大学 | Carbon-coated alpha-Fe2O3Material, preparation method and application thereof |
| CN111774085B (en) * | 2020-07-10 | 2021-12-03 | 复旦大学 | Transition metal carbide/metal organic framework compound and super-assembly preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4883559A (en) * | 1988-04-12 | 1989-11-28 | The United States Of America As Represented By The United States Department Of Energy | Process for making transition metal nitride whiskers |
| US5188130A (en) * | 1989-11-29 | 1993-02-23 | Philip Morris, Incorporated | Chemical heat source comprising metal nitride, metal oxide and carbon |
| CN1593767A (en) * | 2004-06-17 | 2005-03-16 | 大连大学 | Catalyst for preparing high surface area nitride or carbide by plasma method |
| US20050176990A1 (en) * | 2002-02-14 | 2005-08-11 | Monsanto Technology Llc | Oxidation catalyst and process |
| US20060229466A1 (en) * | 2005-02-17 | 2006-10-12 | Monsanto Technology Llc | Transition metal-containing catalysts and catalyst combinations including transition metal-containing catalysts and processes for their preparation and use as oxidation catalysts |
| CN101018632A (en) * | 2002-09-21 | 2007-08-15 | 山特维克知识产权股份有限公司 | Coated metallurgical particles |
| US20070284289A1 (en) * | 2006-04-17 | 2007-12-13 | Petroleo Brasileiro S.A.-Petrobras | Process to prepare mixed molded carbide and nitrite material and its application as a catalyst in hydrotreatment processes |
| WO2009037281A2 (en) * | 2007-09-18 | 2009-03-26 | Basf Se | Method for hydrogenating separation of lignin using transition metal carbides |
| CN102971073A (en) * | 2010-07-01 | 2013-03-13 | 璐彩特国际英国有限公司 | A nitrided mixed oxide catalyst system and a process for the production of ethylenically unsaturated carboxylic acids or esters |
| CN102985177A (en) * | 2010-07-01 | 2013-03-20 | 璐彩特国际英国有限公司 | A mixed oxide catalyst and a process for the production of ethylenically unsaturated carboxylic acids or esters |
| CN104857981A (en) * | 2015-04-24 | 2015-08-26 | 中国科学院山西煤炭化学研究所 | Metal nitride catalyst for acetic acid hydrogenation synthesis of isopropanol and manufacturing method and application thereof |
| CN104968600A (en) * | 2012-08-17 | 2015-10-07 | G·沃格特 | Method for producing transition metal compounds, transition metal compounds and use thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62156264A (en) * | 1985-12-20 | 1987-07-11 | Toyota Central Res & Dev Lab Inc | Surface treatment of iron alloy material |
| JPH03270203A (en) * | 1990-03-20 | 1991-12-02 | Victor Co Of Japan Ltd | Magnetic alloy |
| US5200060A (en) * | 1991-04-26 | 1993-04-06 | Amoco Corporation | Hydrotreating process using carbides and nitrides of group VIB metals |
| JPH0832307B2 (en) * | 1993-03-11 | 1996-03-29 | 東芝タンガロイ株式会社 | Catalyst composition |
| AU2359100A (en) | 1999-01-08 | 2000-07-24 | Trueposition, Inc. | Efficient demodulation techniques for a wireless location system |
| JP4038311B2 (en) | 1999-09-30 | 2008-01-23 | Ｊｆｅエンジニアリング株式会社 | Ammonia synthesis catalyst, production method thereof, and ammonia synthesis method |
| JP2005281768A (en) | 2004-03-29 | 2005-10-13 | Nano Gijutsu Kenkyusho:Kk | Nanocrystal white cast iron powder having high hardness, tough nanocrystal white cast iron bulk material having high hardness and high strength and production method therefor |
| BRPI0601405B1 (en) * | 2006-04-17 | 2017-06-13 | Petroleo Brasileiro S.A. - Petrobras | PREPARATION PROCESS OF MOLDED MIXED PRECURSOR FOR OBTAINING CARBIDE, NITRIDE AND SULFET |
| JP6178758B2 (en) | 2014-06-11 | 2017-08-09 | 日本電信電話株式会社 | Lithium air secondary battery |
-
2017
- 2017-09-12 CA CA3042942A patent/CA3042942C/en active Active
- 2017-09-12 US US16/335,366 patent/US10974962B2/en active Active
- 2017-09-12 CN CN201780061701.8A patent/CN109790024B/en active Active
- 2017-09-12 KR KR1020197009035A patent/KR102453050B1/en active IP Right Grant
- 2017-09-12 SG SG11201901826XA patent/SG11201901826XA/en unknown
- 2017-09-12 EP EP17768654.0A patent/EP3523240B1/en active Active
- 2017-09-12 JP JP2019517957A patent/JP7117296B2/en active Active
-
2019
- 2019-02-22 ZA ZA2019/01134A patent/ZA201901134B/en unknown
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4883559A (en) * | 1988-04-12 | 1989-11-28 | The United States Of America As Represented By The United States Department Of Energy | Process for making transition metal nitride whiskers |
| US5188130A (en) * | 1989-11-29 | 1993-02-23 | Philip Morris, Incorporated | Chemical heat source comprising metal nitride, metal oxide and carbon |
| US20050176990A1 (en) * | 2002-02-14 | 2005-08-11 | Monsanto Technology Llc | Oxidation catalyst and process |
| CN101018632A (en) * | 2002-09-21 | 2007-08-15 | 山特维克知识产权股份有限公司 | Coated metallurgical particles |
| CN1593767A (en) * | 2004-06-17 | 2005-03-16 | 大连大学 | Catalyst for preparing high surface area nitride or carbide by plasma method |
| US20060229466A1 (en) * | 2005-02-17 | 2006-10-12 | Monsanto Technology Llc | Transition metal-containing catalysts and catalyst combinations including transition metal-containing catalysts and processes for their preparation and use as oxidation catalysts |
| US20070284289A1 (en) * | 2006-04-17 | 2007-12-13 | Petroleo Brasileiro S.A.-Petrobras | Process to prepare mixed molded carbide and nitrite material and its application as a catalyst in hydrotreatment processes |
| WO2009037281A2 (en) * | 2007-09-18 | 2009-03-26 | Basf Se | Method for hydrogenating separation of lignin using transition metal carbides |
| CN102971073A (en) * | 2010-07-01 | 2013-03-13 | 璐彩特国际英国有限公司 | A nitrided mixed oxide catalyst system and a process for the production of ethylenically unsaturated carboxylic acids or esters |
| CN102985177A (en) * | 2010-07-01 | 2013-03-20 | 璐彩特国际英国有限公司 | A mixed oxide catalyst and a process for the production of ethylenically unsaturated carboxylic acids or esters |
| CN104968600A (en) * | 2012-08-17 | 2015-10-07 | G·沃格特 | Method for producing transition metal compounds, transition metal compounds and use thereof |
| CN104857981A (en) * | 2015-04-24 | 2015-08-26 | 中国科学院山西煤炭化学研究所 | Metal nitride catalyst for acetic acid hydrogenation synthesis of isopropanol and manufacturing method and application thereof |
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| EP3523240B1 (en) | 2020-10-21 |
| CA3042942C (en) | 2023-01-03 |
| ZA201901134B (en) | 2020-10-28 |
| JP7117296B2 (en) | 2022-08-12 |
| US10974962B2 (en) | 2021-04-13 |
| KR102453050B1 (en) | 2022-10-07 |
| CN109790024B (en) | 2023-04-14 |
| EP3523240A1 (en) | 2019-08-14 |
| JP2019531889A (en) | 2019-11-07 |
| US20190284051A1 (en) | 2019-09-19 |
| KR20190055812A (en) | 2019-05-23 |
| CA3042942A1 (en) | 2018-04-12 |
| SG11201901826XA (en) | 2019-04-29 |
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